Plasticiser alcohol and production improvement

ABSTRACT

Embodiments of the invention disclosed herein relate to a process for the production of a C 6 -C 15  alcohol mixture comprising the steps of: hydroformylating an olefin mixture comprising a branched C 5 -C 14  olefin to form a hydroformylation product comprising aldehydes and formate esters, whereby the hydroformylation product has a net cold sap number from 15 to 38 mg KOH/g, and converting the aldehydes and formate esters to alcohols in a hydrogenation step comprising at least one first hydrogenation reactor comprising a fixed bed of a heterogeneous sulphided bimetallic catalyst.

CROSS REFERENCE TO RELATED APPLICATION

This application is a continuation of Ser. No. 12/767,343, filed Apr.26, 2010, now U.S. Pat. No. 8,143,459 now allowed, which claims thebenefit of Ser. No. 61/183,575, filed Jun. 3, 2009, and Ser. No.61/313,946, filed Mar. 15, 2010, the disclosures of which areincorporated herein by reference in their entireties.

FIELD OF THE INVENTION

The present invention relates to improvements in or relating to theproduction of an improved C6-C15 alcohol mixture, and to esters madefrom such alcohol mixtures. The alcohol mixtures provide improved estersof polycarboxylic acids, in particular phthalate esters, which aresuitable as plasticisers for polymers.

BACKGROUND OF THE INVENTION

C6 to C15 alcohols are produced in large volumes throughout the world bythe hydroformylation of olefins to produce aldehydes, followed byhydrogenation of the aldehydes to produce alcohols. The hydroformylationprocess is also referred to as the Oxo or oxonation process, and thealcohols may also be referred to as oxo-alcohols. The olefins that areused as feeds for the hydroformylation are generally oligomers ofolefins that are obtained from petroleum feedstocks. Various processesmay be used to produce the olefins used for hydroformylation. Forexample, the octenes that are used in the production of nonyl alcohol,which is produced in large volumes for the manufacture of plasticiserester, may be produced by the dimerisation of butenes employing a nickelcontaining catalyst, e.g., by the Octol® or Dimersol® processes, ordimerisation on a zeolite or other acidic catalyst. These are processeswhich yield substantially pure octenes. Alternatively olefin mixturesaveraging about eight carbon atoms may be obtained by theoligomerisation of olefin mixtures using acid catalysts such asphosphoric acid catalysts.

In both these processes, due to the petroleum origin of the olefins, theolefins typically contain impurities such as sulphur and chlorine whichcan have a damaging effect on the hydroformylation reaction and, inparticular, the hydrogenation reactions. The hydrogenation reactions areperformed by catalytic hydrogenation at elevated temperature andpressure and the conditions must be carefully controlled in order tooptimise the yield and selectivity of the hydrogenation, ensure safeoperation of the hydrogenation unit, secure commercially viable catalystlife and minimize side reactions.

Alternative processes for producing alcohols may comprise thehydroformylation of lower carbon number olefins, such as ethylene,propylene and butenes to the corresponding aldehyde or aldehyde mixturescontaining one more carbon number than the starting olefin or olefins.These aldehydes, or mixtures thereof, are then subjected to aldolisationto produce condensation products, typically higher aldehydes containingan extra carbon-carbon double bond, often referred to as enals. Theseenals or enal mixtures may be hydrogenated to the correspondingsaturated aldehydes or aldehyde mixtures, or directly to thecorresponding alcohols or alcohol mixtures. Examples of productsproduced by such processes are 2-methylpentanol, 2-ethylhexanol,2,4-dimethylheptanol and 2-propylheptanol, but other alcohols andalcohol mixtures produced in this way are also known.

Commercial C6-C15 alcohol mixtures may be produced from C5-C14 olefinmixtures by a process involving hydroformylation followed byhydrogenation. Hydroformylation typically uses a homogeneous metalcatalyst, typically rhodium and/or cobalt, often in the carbonyl form.The removal of the metal catalyst may involve oxidizing the metal to awater soluble metal salt. The oxidation may use air as the oxidant.

The subsequent hydrogenation step typically uses a heterogeneouscatalyst. Many hydrogenation catalysts are sensitive to poisoning, inparticular by sulphur, and this often at relatively low levels. If theolefin feed mixtures contain traces of sulphur, it may be preferred toremove the sulphur before the hydroformylation step in order to protecta sulphur sensitive hydrogenation catalyst downstream. This step may beomitted if the selected hydrogenation catalyst is resistant to sulphur.

During the hydroformylation, the aldehydes that are formed by the mainreaction may further react, with H₂ to form the alcohol that is oftenthe prime product, with CO and H₂ to form a formate ester, and with twoalcohol molecules present to form an acetal and water. Water istherefore typically added to the hydroformylation reaction, to promotehydrolysis of formate esters to form an alcohol and formic acid, and/orto push back the acetal formation reaction. In several of the knownhydroformylation catalyst cycles, the formic acid byproduct from thehydroformylation step is a useful component. Part of the formic acidbyproduct may also remain in the hydroformylation product.

The product from the hydroformylation step, typically after removal ofthe metal catalyst, may be routed directly to the subsequenthydrogenation step, or unreacted olefins may first be distilled away andoptionally recycled, and the remainder of the stream may then be fed tohydrogenation, typically including formate esters, acetals and otherheavies.

Also in the hydrogenation step, water is typically introduced, with thepurpose to further promote the reduction of formate ester and/oracetals.

Formate esters may thus also during hydrogenation be hydrolysed andproduce byproduct formic acid. Some hydrogenation catalysts are moreresistant to the presence of formic acid as compared to others. Methanolmay be formed as a byproduct from some of the reactions wherein formateesters are reacted away in the hydrogenation step. We have found thatthe formation of methanol during hydrogenation may depend on the type ofhydrogenation catalyst, on the amount of water present, and on thehydrogenation conditions.

A reduction of the acetals in the hydrogenation step down to low levelsis particularly important because any acetals left in the hydrogenationproduct end up as heavies in the bottom byproduct from the alcoholdistillation step which typically follows downstream. Some hydrogenationcatalysts are better in the removal of acetals as compared to others.

The selection of a hydrogenation catalyst may thus be directed byseveral criteria in addition to its activity in aldehyde hydrogenation.For example, a sulphided bimetallic catalyst in the hydrogenation stepof the alcohol process has good activity in converting formate estersand reducing acetals to very low levels, while withstanding formic acidand sulphur impurities in the hydrogenation feed.

WO 2005/058782 discloses an alcohol process including the hydrogenationof a feed stream having a cold sap number of 38.5 mg KOH/g. The processuses staged water injection in order to improve the reduction of formateesters and of acetals during hydrogenation. WO 2005/058782 proposes touse sulphided bimetallic catalysts because they are not poisoned bysulphur, and proposes to reduce the acidity of the catalyst support inorder to avoid excessive by-product formation. WO 2005/058782 is silentabout any presence or formation of acids, methyl esters or heavy estersprior to or during the hydrogenation step.

U.S. Publication No. 2005/0065384 discloses an alcohol process includingthe hydrogenation of a commercially-obtained crude linear nonanal as thefeed over supported bimetallic catalysts in their reduced and in theirsulphided form. The hydrogenation feeds contain at most 4.5 wt % offormate esters of C9 alcohols, which corresponds to a net cold sapnumber of 14.68 mg KOH/g. U.S. Publication No. 2005/0065384 is silentabout the formation of methanol and methyl esters during thehydrogenation step.

Where aldehydes are present, their corresponding carboxylic acids may beformed via various chemical pathways, such as by reaction with oxygen orby the reaction of two aldehydes with water to form an alcohol plus anacid. Carboxylic acid formation may therefore occur during the differentsteps of the alcohol process, such as during the hydroformylation, thehydroformylation catalyst removal, and the hydrogenation step. We havefound that a sulphided bimetallic hydrogenation catalyst may lead to ahigher carboxylic acid formation as compared to others.

These carboxylic acids are typically undesired in the alcohol productionprocess. Their hydrogenation to alcohol is relatively difficult andslow. Having the same carbon number of the alcohol prime product, theacids are less volatile but remain relatively difficult to separate fromthe prime alcohol product. When distilled away, their downgrade into theheavy byproduct stream represent a loss of useful molecules. Because theseparation by distillation is difficult, the acid containing heavybyproduct may also contain some alcohol, representing further loss ofuseful molecules.

We have also found that hydrogenation catalysts such as the sulphidedbimetallic catalysts may enable esterification. The carboxylic acids maythen react in the hydrogenation step with alcohol to form a heavydi-alkyl ester having twice the carbon number of the alcohol, and water.These heavy esters remain in the bottom of the alcohol distillation andrepresent an even more important loss of useful molecules as compared tothe acid alone.

As methanol may be present during hydrogenation, the esterification ofthe carboxylic acid may also lead to the formation of methyl esters.

We have found that the methyl esters of the carboxylic acids having thesame carbon number of the aldehydes, and thus also of the productalcohol, do not separate from the alcohol product mixture bydistillation, and thus remain primarily as an impurity in the productalcohol mixture. We have also found that it is very difficult to analysefor such methyl esters in a C6-C15 alcohol mixture.

The methyl ester impurity in the alcohol product may cause problems whenthe alcohol product is further esterified to an ester derivative. Aparticular problem occurs when an ester derivative of a polycarboxylicacid or its anhydride is produced, such as a phthalate, an adipate, atrimellitate or a cyclohexane dioate ester. Several of these esters ofpolycarboxylic acids are used as plasticizers for a polymer, typicallyfor polyvinyl chloride (PVC). We have found that during esterification,the methyl ester may be subject to transesterification, freeing up themethanol. The methanol moiety in the methyl ester may be replaced by aparent alcohol moiety and a di-alkyl ester is then formed which has twoalkyl chains with typically the same carbon number as the parent alcoholthat was used for the esterification. We have also found that when anester of a polycarboxylic acid is produced, most of the aliphaticdi-alkyl esters formed during esterification remain as an impurity inthe product ester. This impurity is undesirable because it may increasethe volatility of the ester product, and it may contribute negatively toits performance, such as to the reading in the fogging test, or to thelight scattering film performance, of the plasticiser ester or of anarticle derived there from. This is particularly important for theautomotive industry, but also for other applications such as whenarticles are produced for indoor use.

The methanol that is liberated by the transesterification of the methylester may end up in the water byproduct from the esterification process,where it represents an environmental burden in the disposal of the wastewater. The methanol may also react with the acid or acid anhydride usedin esterification, such as adipic acid or trimellitic or phthalicanhydride, to produce undesirable di-methyl phthalates or adipates, orequivalent di-esters with one methyl and one C6-C15 alkyl group, or atrimellitate with one or two methyl groups instead of the desired alkylgroup with more carbon atoms.

The di-alkyl aliphatic esters that are produced can be carried with thedesired ester during its purification and can remain as an impurity inthe final ester product and large quantities can render the esterunsuitable for use as a plasticiser. Even in smaller quantities, theycan impair the volatility of the plasticiser and affect the foggingperformance of the plasticiser of the finished article producedtherewith. The presence of these undesired esters can be detected andquantified by a GC analysis of the product ester. With phthalate estersfor instance, these di-alkyl aliphatic (mono-)esters elute in the regionthat is called “Intermediates”, i.e., the region of the phthalate esterGC spectrum where the “dimer” impurities elute. Also themethyl-containing tri- or di-esters will tend to elute typically beforethe peak of the main tri- or di-ester, because of their lower molecularweight.

There therefore remains the need for a process for producing an alcoholwherein the formation of carboxylic acids having the same carbon numberas the alcohol is reduced, in particular during the hydrogenation stepand with a sulphided bimetallic hydrogenation catalyst which is moreactive in acetal reduction, which has a better formic acid resistance ora higher resistance to sulphur poisoning. Preferably, also theesterification of such carboxylic acids is reduced. A further needremains for a process to produce an alcohol wherein the formation of themethyl esters of such carboxylic acids during the hydrogenation step isreduced, because of the product quality problems these methyl esters maycreate. There remains also a need for an alcohol that contains only alimited amount of such methyl esters. The downstream process producingan ester derivative from such an alcohol with a polycarboxylic acid, isin need for an alcohol that contains only low amounts of methyl ester,such that the environmental burden associated with disposal of itsbyproduct water is reduced, and also such that its ester productcontains lower amounts of di-alkyl esters and/or di- or tri-estershaving one or more methanol moieties, leading to a product of higherpurity which provides improved performance during downstream processingand improved performance of the derived consumer product during itsuseful lifetime.

SUMMARY OF THE INVENTION

The applicants have found that the formation of carboxylic acids in thealcohol process, and also the methyl ester presence in the productalcohol, may be reduced by a combination of specific controls in thehydroformylation reaction together with other specific controls in thesubsequent hydrogenation reaction step.

The invention therefore provides a process for the production of aC6-C15 alcohol mixture comprising the steps of:

-   -   a. hydroformylating an olefin mixture comprising a branched        C5-C14 olefin to form a hydroformylation product comprising        aldehydes and formate esters, whereby the hydroformylation        product has a net cold sap number from 15 to 38 mg KOH/g, and    -   b. converting the aldehydes and formate esters to alcohols in a        hydrogenation step comprising at least one first hydrogenation        reactor comprising a fixed bed of a heterogeneous sulphided        bimetallic catalyst, optionally followed by at least one second        hydrogenation reactor connected downstream of the first reactor,        wherein the feed to the hydrogenation step (b) is a liquid        comprising at least a portion of the aldehydes and formate        esters formed in step (a) and at least 2 wt % water, based on        the liquid hydrogenation feed, and wherein the temperature in        the first hydrogenation reactor is at most 200° C., preferably,        from 150° C. to 200° C., more preferably in the range of from        160° C. to 180° C.

The process according to the invention produces the alcohol by firsthydroformylating an olefin mixture to a product having a net cold sapnumber within a specified range, followed by a downstream hydrogenationstep wherein the formation of carboxylic acids, and indirectly also ofany heavy di-alkyl esters and/or methyl esters thereof, is controlled bya combination of a tight control of the water addition and of thereactor temperature.

The net cold saponification (in short also called net “cold sap”) numberis a measure for the presence of formate esters in the hydroformylationproduct. The presence of formate esters in the hydrogenation feedaffects the amount of methanol that may be formed during thehydrogenation step. The controls in the hydrogenation step then lead toa controlled make of additional carboxylic acid, and thus to a lowerpresence of carboxylic acids in the hydrogenation step. With less acid,less of the di-alkyl esters are formed, and less associated yield lossis suffered. With less acid and less methanol, less methyl esters areformed in the hydrogenation step providing a product alcohol ofincreased purity. The water added further affects the esterificationequilibrium, thereby further reducing the levels of heavy di-alkylesters and of methyl esters in the hydrogenation product, bringingadvantages in terms of alcohol product yield and quality.

In another embodiment, the invention provides a C6-C15 alcohol mixturecontaining at most 300 ppm by weight of methyl esters of C6-C15carboxylic acids, preferably at most 250 ppm by weight, more preferablyat most 200 ppm, yet more preferably at most 150 ppm, even morepreferably at most 100 ppm and most preferably at most 50 ppm by weight.

This brings several advantages. For example, an esterification processusing the alcohol according to the invention liberates less methanolfrom the transesterification of the methyl esters, such that lessmethanol ends up in its byproduct water, and the ester process thusenjoys a reduced environmental burden in the disposal of its wastebyproduct water.

Also, the ester derivative of the alcohol of the invention with apolycarboxylic acid contains a limited amount of di-alkyl aliphaticmono-esters.

In yet another embodiment, the invention therefore provides a C6-C15ester of a polycarboxylic acid containing C6-C15 di-alkyl aliphaticmono-esters in an amount less than the amount that may be generated bytransesterification of the methyl esters in the alcohol mixture that isused in the esterification. The ester of the polycarboxylic acidpreferably is a phthalate di-ester, an adipate di-ester, a trimellitatetri-ester, or a cyclohexanoate di-ester. The aliphatic di-alkyl estershave a number of carbon atoms in their acid moiety that is the same asthe number of carbon atoms in the parent alcohol used in esterification,and the alcohol moiety has also that same number of carbon atoms.

The polycarboxylic acid for the ester according to the invention ispreferably selected from phthalic acid, adipic acid, trimellitic acid,cyclohexane dicarboxylic acid, and the anhydrides thereof. When thereare 200 ppm by weight of methyl esters present in the parent C6-C15alcohol of the polycarboxylic acid ester production, the correspondingmaximum possible amount of C6-C15 di-alkyl aliphatic mono-esters in thepolycarboxylic acid ester can be calculated, and depends on the carbonnumber of the parent alcohol and on the nature of the polycarboxylicacid ester produced. The 200 ppm by weight of methyl esters may lead toat most the ppm by weight of di-alkyl aliphatic mono-esters in thepolycarboxylic acid esters as shown in Table 1. The levels of di-alkylaliphatic mono-esters corresponding to higher and lower levels of methylesters can be calculated proportionally from the numbers in Table 1.

TABLE 1 ppm by weight di-alkyl ester Polycarboxylic acid ester AlcoholPhthalate Adipate Cyclohexanoate Trimellitate Carbon Number di-esterdi-ester di-ester tri-ester 6 187.9 199.9 184.6 203.8 7 202.9 214.8199.6 218.7 8 216.0 227.7 212.8 231.5 9 227.5 239.0 224.3 242.6 10 237.7248.9 234.5 252.4 11 246.8 257.6 243.7 261.1 12 254.9 265.4 251.9 268.813 262.2 272.4 259.2 275.7 14 268.8 278.8 265.9 281.9 15 274.8 284.5272.0 287.5

The polycarboxylic acid ester according to the invention has a lowervolatility and thus a higher permanence, and shows an improvedperformance in fogging or light scattering film tests. Flexible PVCarticles produced with the ester according to the invention also enjoythe higher permanence of the plasticizer and the improved performance infogging, light scattering film, or indoor volatility tests such as theFLEC or Nordtest.

The process according to the invention provides several furtheradvantages.

Having less formate esters formed in hydroformylation consumes lesssynthesis gas in the hydroformylation step. Having less formate estersin the feed to hydrogenation also leads to a reduced formation of COand/or CO₂ byproducts. CO may negatively affect the activity of somehydrogenation catalysts. The byproducts are gaseous components ending upin the offgasses from the hydrogenation process, making them less purein hydrogen, and therefore less suitable for recycle to thehydrogenation process. The byproducts build up in the process whenrecycled, and the molecular weight of the hydrogenation offgas increaseswith more CO and/or CO₂, which increases the duty of the compressorrequired for any offgas recycle. Separating the useful H₂ from theundesired CO and/or CO₂ in the offgasses is typically not economical.With less CO and/or CO₂ to dispose of, typically also less useful H₂ hasto be discarded together therewith.

DETAILED DESCRIPTION

Hydroformylation is a well-known process in which an olefin is reactedwith carbon monoxide and hydrogen in the presence of a catalyst to formaldehydes and alcohols containing one carbon atom more than the feedolefin. This process has been operated commercially for many years andthere have been two principle technology families used, one of which isknown as the low or medium pressure oxo process family and whichgenerally involves the use as catalyst of an organometallic complex ofrhodium with organophosphorous ligands for providing the necessarystability at the lower pressures and operates at pressures from 10 to100 Bar. The second process family is known as the high ormedium-pressure process family and generally involves the use of anunmodified cobalt or rhodium based catalyst and typically operates atpressures from 100 to 350 Bar. Generally the low pressure processes areused for the hydroformylation of unbranched and terminal, primarilylower olefins such as ethylene, propylene and n-butenes, but alsoincluding n-hexene-1 and n-octene-1, or surfactant range Fischer-Tropscholefin mixtures, whereas the high or medium pressure processes areprimarily used for the hydroformylation of linear and/or branched higherolefins or mixtures such as those containing 5 or more carbon atoms.This process is widely used to produce what are known as “higheralcohols” or aldehydes or acids which are in the C6-C15 rangeparticularly the C9-C13 range. The present invention is particularlyapplicable to the high pressure cobalt catalysed hydroformylationprocess since the production of formate esters is particularly high whenthat technology is employed.

The hydroformylation typically uses a homogeneously dissolved catalystcomplex, which may be based on cobalt or rhodium, and sometimespalladium. Ligands may be used to modify the catalyst complex, usuallybeing phosphorous based, and tributylphosphine is typically known to beused with cobalt metal. With rhodium, the ligands are typicallyorganophosphines, with triphenylphosphine (TPP) or the oxide thereofbeing preferred, or organophosphites.

Where cobalt catalysed hydroformylation is used, the product isdecobalted. In one embodiment, this is done by neutralising the activecobalt species HCo(CO)₄, with a base such as sodium hydroxide orcarbonate in a decobalter. The decobalter conditions are such that theneutralization converts the hydrocobalt carbonyl to sodium cobaltcarbonyl. Preferred conditions are to use a stoichiometric excess ofsodium hydroxide or carbonate above the amount needed for cobaltneutralization, an excess of 100% to 200% particularly 140% to 180% isuseful. The decobalter is typically operated at a temperature in therange 155° C.-165° C. and it is preferred that sufficient carbon dioxideand/or carbonate is present in the decobalter to ensure the formation ofsodium cobalt carbonyl and to also buffer the pH in the range 7.8 to8.5. This technique is described in more detail in WO 2006/122526.

Alternative embodiments use techniques for the decobalting of theproduct of cobalt catalysed hydroformylation by oxidative methods, andare described in WO 2008/128852, which are conveniently used togetherwith the techniques of the present invention. Yet, other suitabletechniques are described in U.S. Pat. Nos. 5,237,105, 5,218,134, and4,625,067, and in copending patent application U.S. Ser. No. 61/092,835,and yet another suitable technique is described in copending patentapplication U.S. Ser. No. 61/092,833.

The preferred conditions for hydroformylation are described in WO2005/058787 and these are preferably used in the present invention.

In order to improve the selectivity of the hydroformylation reaction,water may be present in the hydroformylation reactors. We have foundthat the injection of water reduces the formation of formate esters andheavy by-products. When used, water should be injected into the firstreactor, and may also be injected into the second and subsequentreactors, if they are used, but we have found that this is not alwaysessential. In a gas-lift reactor, the formation of a significant volumeof a stagnant free water phase in the bottom can become an impediment oreven an obstruction to the circulation of the reactor fluid. Gas-liftreactors from which any free water is continuously removed from thebottom have been described in WO 01/14297. If there is no water removalcapability, the quantity of water that is introduced should preferablynot exceed or not exceed by more than 10% or 20% the solubility of thewater in the reaction mixture, to avoid the formation of a stagnant freewater phase in the reactor. We have found that no more than 2 wt % ofwater based on the weight of olefin feed should be used in the firsthydroformylation reactor and typically from 1.0 wt % to 1.75 wt %particularly 1.5 wt % should be used. The weight of the olefin feedbeing the weight of unsaturated materials in the feed which is typicallyabove 95 wt % of the feed and frequently about 99 wt % of the feed.Where water is injected into the second reactor, similar considerationsmay apply depending on the design of the reactor. Due to the differentliquid composition in the second reactor, the water solubility may bedifferent in this reactor, and we prefer to use typically a total of 2.5wt % water present based on the olefin feed. These amounts of waterapply readily in the production of C6-C11 alcohols. They may have to bereduced for the production of heavier alcohols because of the lowerwater solubility of their hydroformylation reaction mixtures.

We have found that the injection of water provides a significantimprovement in plant utilization as well as carbon monoxide utilization.The water should be injected in a manner that ensures good mixing of thewater with the reactants and also prevents large fluctuations in theolefin to water feed ratios.

Accordingly, it is preferred that the water be injected into a fullyoperational reactor and when a loop reactor is used, it is preferredthat the materials are circulating at a velocity of at least 0.6meters/sec when the water is injected. It is also preferred that thewater and the olefin are continuously introduced into the reactor at thedesired water to olefin ratio.

In preparation for the hydrogenation phase the product fromhydroformylation is preferably cooled, passed to a decobalting ordemetalling and washing unit, filtered to further remove cobalt speciesand the use of pumice filters is particularly preferred for the removalof cobalt. At this stage the water content of the hydroformylationproduct is typically between 1 and 3 wt % water, which may be dissolvedand/or in the form of entrained droplets. The presence of free waterdroplets by entrainment, such from the washing unit, may be furtherreduced by the use of a water coalescer. More details on a coalescer aredisclosed in our copending application U.S. Ser. No. 61/092,833. Thetemperature of the product at this stage is typically between 40° C. and80° C., more typically between 50° C. and 70° C., and especially 60° C.The product is then fed (with any further water addition if needed) tothe first hydrogenation reactor. It may be preferred that the productpasses in an upward direction through the first hydrogenation reactorsince this flow mode results in improved heat transfer. Upward flowhowever increases the risk for water buildup in the reactor, in case afree water phase would exist. Downward flow may be preferred to avoidthe risk for water layer buildup, and may also provide a better liquidand gas distribution under well defined hydraulic conditions, asexplained in WO 2006/086067.

We have found that under the conditions in the first hydrogenationreaction in the process according to the invention, the aldehydes arehydrogenating fast to the corresponding alcohol, while the formation ofacids is reduced. We believe that this beneficial effect is obtained bykeeping the temperature in the first hydrogenation reactor limited tothe specified maximum. This may be achieved by any of a series processfeatures, such as a lower reactor inlet temperature or a partial recycleof the product of the first hydrogenation reactor, or of thehydrogenation product. Using partial recycle of a hydrogenation reactorproduct or the product of the hydrogenation section to the feed of thehydrogenation section has, in addition to its first benefit by dilutionon lowering the reaction exotherm, a significant further advantage.While the aldehyde hydrogenation reaction rate is first order inaldehyde concentration, the acid formation via the Cannizzaro reactioninvolves two aldehyde molecules and is therefore second order inaldehyde concentration. The positive effect of the dilution on reducingthe acid formation rate via the Cannizzaro reaction may thus be muchstronger than the negative effect on the aldehyde hydrogenation rate.The intermediate or product recycle brings further the additionaladvantage that the water solubility of the total hydrogenation feed isincreased, such that any entrained or injected water more readilydissolves into the organic stream, thereby reducing the risk of exposingequipment and/or catalyst to a free water phase, which may possiblybuild up inside the equipment, especially in a reactor operating inupflow mode, and which may cause corrosion of the equipment. A preferredhydrogenation section intermediate recycle operation is described inmore detail in U.S. Pat. No. 4,877,358.

The preferred amount of water present during hydrogenation is a carefulbalance. On the one hand, a higher water presence may tend to increasethe formation rate of acids from aldehydes, which is a disadvantage. Onthe other hand, a higher water presence favourably affects theequilibrium between acids and their esters, in this case both heavydi-alkyl esters and methyl esters. We have found that a minimum of 2 wt% of water in the feed to the first hydrogenation reactor is preferred,and that preferably a maximum of 3 wt %, based on the liquidhydrogenation feed, should not be exceeded. This balanced amount ofwater keeps the acid production under control, and also reduces theappearance of esters thereof in the product of the first hydrogenationreactor, and further downstream in the hydrogenation product. We preferto include a second hydrogenation reactor downstream of and connected inseries with the first hydrogenation reactor. Preferably this secondhydrogenation reactor is loaded with a hydrogenation catalyst of thesame type as in the first hydrogenation reactor. We prefer to operatesuch a second hydrogenation reactor at a higher temperature than thefirst hydrogenation reactor, preferably using a temperature of at least180° C., more preferably in the range of from 190° C. to 210° C.,typically at around 200° C. We have found that a higher temperature inthe back end of the hydrogenation step brings the advantage of reducingthe presence of acids, methyl esters and/or of heavier di-alkylmono-esters in the product of the hydrogenation step. This reduces theloss of valuable molecules by esterification in the bottom of any of thedownstream distillation towers, and the loss of these heavier estermolecules with the heavy byproduct from such distillation. It alsoreduces the methyl ester content in the alcohol product afterdistillation.

We prefer to use in the first hydrogenation reactor a pressure of atleast 55 barg, preferably at least 60 barg. This provides sufficientpartial pressure of hydrogen to drive the hydrogen consuming reactions.More preferably, we use a pressure of at least 120 barg, even morepreferably at least 125 barg. At the higher pressure, we have found thatthe acid make is reduced, and thereby the loss of valuable molecules asdi-alkyl esters in the heavy byproduct from distillation. A higherpressure, however, may lead to a higher methanol make from the formateesters in the hydrogenation feed, which may lead to a higher methylester content in the hydrogenation product, and thus in the productalcohol. We also prefer to use a pressure that is not more than 130barg. Further pressure increases were found to have only negligibleeffects, while they further increase the investment cost of theequipment.

In a preferred liquid phase hydrogenation process, the product from thefirst hydrogenation reactor then passes in a line to the secondhydrogenation reactor and it is preferred that the line be provided withan inlet for the injection of water and a mixer whereby the water andthe product may be mixed to ensure that the water is dissolved and/orentrained in the product. It is preferred that from 1 wt % to 2 wt % ofwater based on the weight of the product be injected. The mixture thenpasses to the second hydrogenation reactor where it passes through thecatalyst bed at a temperature of 180° C. to 210° C. in the presence ofhydrogen. In the preferred embodiment the product flows downwardly inthe second reactor.

Following the last hydrogenation reactor the product passes to a highpressure separator in which unreacted hydrogen may be flashed off and,if desired, recycled to the hydroformylation reactors as is described inWO 2005/058787. It is also possible to recycle some or all of thisunreacted hydrogen to the hydrogenation reactors. In this embodimentonly a portion of the unreacted hydrogen is passed to thehydroformylation reactors.

The product of hydrogenation following the separation of the hydrogencomprises a mixture of the desired alcohols, olefins and paraffins,alcohol dimers, acetals and traces of aldehydes and formates togetherwith dissolved carbon dioxide and dissolved hydrogen and water, andaliphatic esters of carboxylic acids. The product may then be purifiedfirstly through a coalescer to remove water, followed by fractionaldistillation to separate the C6-C15 alcohol from the lower boilingfraction of the mixture and a second distillation to separate thealcohol from the higher boiling fraction. Water and any methanol orother lower alcohols typically will be separated with the lower boilingfraction, and may settle out as a separate phase in the tower overheadsystem, from where they can be discarded or taken for further use. Thepresence of methanol can cause environmental problems requiring specialdisposal techniques and accordingly the reduction in the production ofmethanol according to the present invention is particularly beneficial.

Particularly with liquid phase hydrogenation, the hydrogenation reactorsmay be vertical tubes, provided with a jacket for temperature controland heat removal. They may be operated in upflow or in downflow mode. Inthe jacket, water or another suitable cooling medium such as an alkanol,preferably methanol, may be circulated using a pumparound system fromwhich hot cooling medium may be withdrawn, and to which cold coolingmedium may be supplied. Each reactor may be provided with a so-calledconditioner, which is a heat exchanger one side of which is part of thecooling medium circulation, and which on the other side is forconditioning the reactor feed to the appropriate temperature before itpasses to the reactor itself. Conditioning of the reactor feed isespecially important when a reactor that is not a lead reactor containsrelatively fresh and active catalyst, and therefore needs to be operatedat start-of-run conditions, this typically requires a lower temperature.The upstream reactor on the other hand, may contain partiallydeactivated catalyst and therefore needs to be operating at mid-of-runor end-of-run conditions, which may require a higher temperature. Feedconditioning can therefore avoid a reactor feed that is too hot for anactive catalyst to handle, and can therefore reduce the risk fortemperature runaway.

In gas phase hydrogenation, the reactors may contain one of more fixedbeds of catalyst, and cooler fresh or recycle hydrogen may be injectedin the reactor, its feed or in between the catalyst beds in the reactorfor temperature control.

The process according to the invention provides the additional benefitthat it operates close to the economic optimum olefin conversion withrespect to overall variable costs.

In hydroformylation the main reaction is the olefin reacting with CO andH₂ to form an aldehyde having one carbon atom more than the startingolefin. The hydroformylation reaction rate is first order with respectto olefin concentration. This was clearly demonstrated for pure olefins.When olefin mixtures are hydroformylated, especially those mixtures thatare rich in branched olefins, not all olefins react at the same rate dueto differences in the location of the olefinic bond and in branchiness.The apparent overall reaction rate on such mixtures may thus deviatesignificantly from first order. As a result, one percent extra olefinconversion is much more difficult to obtain at a higher olefinconversion level.

Minor amounts of olefins may react with H₂ to form paraffins. Theparaffins formed have about the same boiling point as the startingolefins. In a boiling point GC of the hydroformylation product, theseparaffins do not show separately from any unreacted olefins or fromparaffins that were already present in the hydroformylation feed. It istherefore convenient, and standard practice, to express the olefinconversion for a hydroformylation process as “Conversion Ex Paraffin”,i.e., excluding any paraffin make, thus without accounting for theolefins that may have converted to paraffins. This olefin conversion “ExParaffin” or “Ex Par.” can readily be determined by boiling point GCanalysis, and is a handy and useful tool in measuring the progress ofthe hydroformylation reaction. When the hydroformylation product ispassed on without intermediate distillation to the subsequenthydrogenation step, the olefin conversion Ex Par may also be determinedfrom a boiling point GC spectrum of the hydrogenation product. It istherefore a useful tool in monitoring the overall alcohol productionprocess.

The aldehyde formed by the hydroformylation of an olefin may be thesubject of consecutive reactions. The aldehyde may for instancehydrogenate to form an alcohol, and this reaction may be favourable whenthe alcohol is the desired product. Another consecutive reaction iswhere the aldehyde undergoes a second reaction with CO and H₂,converting the aldehyde to a formate ester:R—CH═O+CO+H₂→R—CH₂—O—CH═O

The aldehyde molecule in the formate ester is not necessarily lost fromthe alcohol production process. The formate esters may for instance behydrolysed with water to form the desired product alcohol and formicacid:R—CH₂—O—CH═O+H₂O→R—CH₂—OH+HCOOH

Minor amounts of water are typically added to the hydroformylationreaction and to the subsequent hydrogenation step for this purpose.

The formate esters are also recoverable as alcohols in the subsequenthydrogenation step, by a second pathway called hydrogenolysis, wherebymethanol, CO, H₂ and/or CO₂ may be formed as byproducts, e.g., asfollows:R—CH₂—O—CH═O+2H₂→R—CH₂—OH+CH₃OH

While the formation of formate esters during hydroformylation thus doesnot necessarily represent a loss of aldehydes for the production ofdesired alcohols, it does represent an additional consumption of CO andH₂ in the hydroformylation step, and the extra synthesis gas ends up asformic acid, methanol, CO, H2 and/or CO₂ further downstream. Only the H₂byproduct may be considered useful, as it is liberated in thehydrogenation step where it supplements the H₂ gas added and participatein the hydrogenation reaction.

In the hydroformylation process, other consecutive reactions formheavies, such as ethers and ether-alcohols, many of which are notrecoverable, or at least not as readily recoverable, as product alcoholsand end up in the heavy oxonation fraction byproduct of the alcoholprocess. The heavy byproduct typically demands a lower economic returnthan the olefin feedstock or the light oxonation fraction byproductcontaining the unreacted olefins. Their formation is thus typicallyundesirable in view of the process economics.

The various consecutive reactions involving aldehydes increase in rateas the aldehyde content of the reaction mixture increases. They becomethus more important at higher conversions of the feed olefins. Whenolefin conversion is pushed up in a hydroformylation process, anoperating point is reached where there is no more additional economicgain in converting more of the olefin feed, mainly because of theassociated additional production of heavy byproduct. That operatingpoint defines the economic optimum olefin conversion. The optimum olefinconversion depends on the type of olefin mixture. We have found howeverthat, irrespective of the type of olefin feed, when the conversion ofolefins is around its economic optimum for that feed type, theconcentration of formate esters in the hydroformylation producttypically is in the same range. We have found that the net cold sap of ahydroformylation product around the economic optimum of the overallprocess is in the range of from 15 to 38 mg KOH/g, more preferably inthe range of from 16 to 35 mg KOH/g, even more preferably in the rangeof from 17 to 33 mg KOH/g, yet more preferably of from 18 to 30 mgKOH/g, and even more preferably in the range from 19 to 27 mg KOH/g,most preferably in the range of from 20 to 25 mg KOH/g.

Formate esters in a hydroformylation product can readily be measured bydetermining the cold saponification (“cold sap”) number, using awell-known technique, such as based on ASTM D94 or DIN 51559. The rawcold sap number is a result of a potentiometric back titration. First,the free acids and the formate esters in the sample are saponified withan excess of KOH, preferably in ethanol as solvent. A selectivehydrolysis of the formate esters is achieved by performing thesaponification at room temperature. The back titration is typicallyperformed with HCl, and the result is then conveniently converted to mgKOH/g. We have found that the raw cold sap number is not affected by thepresence of methyl esters or heavier esters, as these do not appear toundergo hydrolysis at room temperature. A true measure of only theformate ester content is then obtained by deducting from the raw coldsap number the contribution of any free acids that were already presentin the sample, to obtain the net cold sap number. The contribution ofthese acids to the raw cold sap number is readily determined bymeasuring the sample acidity, typically by a simple titration method,such as based on ISO standard 1843/2, and expressing the result in thesame units, i.e., also in mg KOH/g.

A hot saponification number may also be determined by a method based onASTM D94. In the hot sap method, all esters are hydrolysed by performingthe saponification step with the excess KPH under ethanol solvent refluxconditions. The result from the titration is the raw hot sap number,which includes all free acids already present in the sample plus allacids obtained from hydrolysis of all esters, including the formateesters, the methyl esters, and the heavier esters. A net hot sap numberis obtained by deducting the amount due to the free acids alreadypresent in the starting sample. In order to evaluate hydrogenationperformance, we like to determine sample acidity, raw cold sap numberand raw hot sap number. The raw cold sap number minus the acidity thengives the net cold sap number. The raw hot sap number minus the raw coldsap number gives a measure for the total presence of methyl esters plusheavier esters. Adding the acid number to this total then gives what welike to call “the total acid number”, a useful measure of the totalexpected loss of useful molecules, assuming that the acids and heavyesters are distilled away from the alcohol during downstreamdistillation, and including also the methyl esters that remain in theproduct alcohol. We like to use this “total acid number” as guidance toevaluate and compare different hydrogenation performances.

The amount of water present in a liquid organic stream such as thehydroformylation product or the hydrogenation feed stream in the processaccording to the invention may be readily determined using a methodknown in the art. We prefer to use the Karl-Fischer titration method orequivalent for this purpose, because of its high accuracy.

The amount of methyl esters present in an alcohol mixture may bedetermined by Gas Chromatography combined with Mass Spectrometry (GCMS),preferably by the EI-GC-MS method. EI or EI+ stands for Electron ImpactIonization. We believe that the methyl ester molecules in the massspectrometry undergo a McLafferty rearrangement, selectively forming asa major fragment a molecule fragment that is rather specific for themethyl ester and which has a molecular weight of 74. Without being boundby theory, we believe the fragment formed is CH₃—O—COH═CH₂. Thisfragment is believed to be formed independent of the structure andcarbon number of the alkyl chain of the acid moiety of the methyl ester.We prefer to use a polar column for the GC, such as the FFAP type columnfrom a supplier such as Hewlett Packard, in which methyl esters tend toelute ahead of alcohols having the same alkyl chain, and we prefer tointegrate all the peaks giving the 74 molecular weight fragment in theGC region where alcohol molecules or their precursors elute. The totalpresence of methyl esters in an alcohol mixture sample may be readilyobtained by this integration. The accuracy of the method depends on agood separation of peaks in the GC, and we prefer to use a GC column of50 m×0.32 mm ID×0.5 μm, an oven temperature starting at 60° C. andincreasing to 130° C. at a rate of 5° C. per minute, and furtherincreasing to 240° C. at a rate of 25° C. per minute. We prefer to usean injector temperature of 250° C., a constant flow volume of 1.5 ml/minof Helium as the carrier gas, a split ratio of 1/150 and an injectionvolume of 1.0 μl. For the Mass Spectrometry, we prefer to use interfacetemperature of 240° C. and a full scan acquisition with 5.0 scans persecond. We prefer the full scan above a Single Ion Monitoring (SIM)approach, because it allows to verify whether the peak giving the 74molecular weight fragment is most likely a methyl ester. This allowsweeding out any alcohol peaks that may also have given a 74 molecularweight fragment as a minor fragment. For a C9 alcohol mixture, we preferto use a scan range (expressed in atomic mass units (a.m.u.)) of 35-200and to start the acquisition at 4.5 minutes and stop it at 15.5 minutes.

We have found that for relatively complex mixtures of isononyl alcohols,a detection limit of 200 ppm by weight in total is readily achievable.By improved parameter tuning this detection limit may be further reducedto 50 ppm by weight or below. For more simple mixtures of isononylalcohols, such as the isononyl alcohols derived from octenes obtainedvia the Octol® or Dimersol®-X process, the detection limit may be lower,down to the level of about 10 or 20 ppm by weight. For a furtherimproved accuracy and lower detection limit, a two dimensional MS-MStechnique may be applied.

We have found that these EI-GC-MS methods to determine methyl estercontent in alcohol mixtures are fast and have a low detection limitcompared to alternatives. The drawback is that there may be methylesters present having a branch on the second carbon of their acidmoiety, in which case the corresponding fragment produced in the MassSpectrometry has a molecular weight that is different from, i.e., higherthan 74. These methyl esters are then not detected with the abovemethod, but we have found that their presence is usually small and mayfor practical purposes be neglected in most circumstances, except whenthe aldehydes to be hydrogenated are produced by aldolisation, in whichcase practically all of the molecules have a branch in their alkyl chainon the second carbon from the oxygen atom.

We have found that the presence of methyl esters may also be determinedby ¹³C-NMR. This NMR method is not affected by any branching on thesecond carbon, and may thus be more selective and more appropriate foralcohols made by a process including aldolisation. Because of the lowersensitivity, a quantitative ¹³C-NMR method may require a longaccumulation time, such as at least 10 hours.

We have found that on a scale of 0 to 220 ppm relative to tetramethylsilane (TMS), and using deutero acetone instead of the more typicaldeutero chloroform (CDCL₃) as solvent, the methoxy group of the methylester can be detected between 51.2 and 51.4 ppm, and that this isseparate from the resonances of the methoxy group of methanol and methylethers. Because other peaks, such as a CH₂ group between two branches,can also be present in the 50 to 52 ppm region, we prefer to complementthis measurement with another experiment, named DistortionlessEnhancement by Polarization Transfer (DEPT). This additional experimentleads to 4 different spectra, showing specifically methyl, methylene,methine and all the protonated carbons, and from which it is possible todetect selectively the CH₃ peak from the methoxy group, even in acrowded region of the spectrum. All other methyl groups arising from thealkyl chains are detected between 31 and 5 ppm and do not interfere.Quantification can be done relative to the integration of the ethoxyfunction of the alcohols, appearing between 60 and 72 ppm, and by takinginto account the molecular weight of the alcohol and of the methylester. A detection limit of 200 ppm by weight was readily obtained, anda longer acquisition time may further increase the sensitivity of themeasurement.

We prefer to include into the process according to the invention anadditional step, preceding the hydrogenation step (b), for reducing thelevel of formate esters in the liquid feed to the hydrogenation step(b). Having less formate esters in the hydrogenation feed will reducethe formation of methanol during hydrogenation, and therefore lead to alower presence of methyl esters in the hydrogenation product, and thusalso in the product alcohol mixture.

We prefer to reduce the format esters in the feed to hydrogenation byhydrolysis. This may for instance be achieved by contacting the productof the hydroformylation step (a), or the feed to the hydrogenation step(b), in the presence of water and preferably also of hydrogen, withalumina (Al₂O₃). On the alumina, the formate esters will at least partlyhydrolyze to the alcohol plus formic acid, and the formic acid maydecompose to CO plus water. Suitable conditions for the hydrolysis stepare described in U.S. Pat. No. 3,935,285 for the hydrolysis of formateesters, and in U.S. Pat. No. 5,059,718 and U.S. Pat. No. 4,401,834 asdescribed for the hydrolysis of acetals. U.S. Pat. No. 3,935,285describes the distillation of a decobalted C9 hydroformylation productobtained from diisobutylene, and treating the distillation bottomproduct containing 15% of formic acid esters of the C9 alcohols withwater at 300° C. over alumina to obtain hydrolysis, and hydrogenatingthe treated product using a nickel catalyst. The presence of 15% formicacid esters of C9 alcohol corresponds to a net cold sap number of 48.9mg KOH/g. In U.S. Pat. No. 4,401,834 the presence and variation of acidsand total esters in the process streams is monitored by giving acidnumber and the ester number as determined by the hot saponificationmethod.

We have also found that cuprous chrome catalyst, such as described in WO2005/058782 and exemplified by G 22 RS available from Süd-Chemie and Cu1155 T available from Engelhard, now BASF catalysts LLC, is aparticularly suitable catalyst to hydrolyse formate esters, even in itsspent or poisoned form when its activity for aldehyde hydrogenation hasalready significantly been reduced. The advantage of using a cuprouschrome catalyst for formate ester hydrolysis is that the breakdown ofthe formate ester generates additional hydrogen, together with CO₂. Theliberated hydrogen then becomes readily available for hydrogenation ofan aldehyde, so that less hydrogen is needed in the hydrogenation stepand it may be operated with a lower stoichiometric excess, but also apart of the aldehydes in the hydrogenation feed stream may already behydrogenated in the formate ester hydrolysis step, thereby reducing theexotherm in the first hydrogenation reaction. All these factors areleading to a lower acid make on the sulphided bimetallic catalyst in thehydrogenation reactors, primarily in the first one. Additional hydrogenmay be added in a hydrolysis step that uses a catalyst that alsocatalyses the hydrogenation reaction, such as the cuprous chromecatalyst. We prefer to operate the cuprous chrome hydrolysis step at apressure of from 50 to 60 barg, preferably 55 barg, because at higherpressures the hydrolysis step may produce more methanol byproduct.

In one embodiment of the invention, the level of formate esters isreduced by contacting the liquid feed to the hydrogenation step (b) witha cuprous chrome catalyst in the presence of hydrogen and at least 2 wt% of water, based on the total liquid feed.

Sulphided bimetallic hydrogenation catalysts suitable for the processaccording to the invention are disclosed in WO 2005/058782, U.S.Publication No. 2005/0065384, U.S. Pat. No. 5,306,848, U.S. Pat. No.6,278,030, or U.S. Pat. No. 5,382,715. We prefer to select a catalystfrom the group consisting of sulphided Co oxide/Mo oxide, sulphidedNi/W—O, and sulphided Ni oxide/Mo oxide. Such catalysts are typicallyproduced in their metal oxide form but are then sulphided with a sulphurprecursor such as alkyl sulphides but preferably H₂S, to form theactivated catalyst in its sulphide form. Also particularly suitable arethe reduced nickel-molybdenum catalysts, e.g. carried on aluminasupport, that are disclosed in X. Wang et al, “Characterization ofActive Sites over Reduced Ni—Mo/Al₂O₃ Catalysts for Hydrogenation ofLinear Aldehydes”, J. Phys. Chem. B 2005, 109, pp. 1882-1890, whichcatalysts we have found are also suitable for hydrogenation for branchedaldehydes. These catalysts preferably contain no, or only small amountsof phosphorus, such as 0-1.0 wt % P, more preferably 0-0.5 wt % P, asdisclosed in U.S. Pat. No. 5,382,715. Most preferably they aresubstantially free of phosphorus, as disclosed in U.S. Pat. No.5,399,793.

We prefer to convert as much as possible of the aldehydes in the firsthydrogenation reactor under the specified conditions, in order tosuppress acid formation and thereby the formation of methyl esters andheavy esters. Over time the hydrogenation activity of the catalyst inthe first hydrogenation reactor will decrease to below its initialactivity. The temperature in the first hydrogenation reactor may then beincreased to compensate for that loss of activity, but we prefer to staywithin the limits specified. The loss of catalytic activity in the firsthydrogenation reactor may then lead to an increase of methyl esterspresent in the product alcohol. When the level of methyl esters in theproduct alcohol becomes unacceptable, we prefer to introduce a thirdhydrogenation reactor into the process, comprising a heterogeneoussulphided bimetallic catalyst having a higher hydrogenation activitythan the catalyst in the first hydrogenation reactor, and we prefer tointroduce this third hydrogenation reactor into service as part of theprocess connected to and in series upstream of the first hydrogenationreactor. The first hydrogenation reactor then becomes situated in secondor in tail end position, and its hydrogenation conditions may beadjusted accordingly and similar to those in the second hydrogenationreactor.

Also the catalyst activity in the second hydrogenation reactor mayreduce over time. Subsequent to the introduction of the thirdhydrogenation reactor, the first or the second hydrogenation reactor maybe removed from service as part of the process. This decommissioning maybe followed by a regeneration of the catalyst in the hydrogenationreactor removed from service, or by a replacement of its catalyst with aregenerated or a fresh catalyst of the same type.

The alcohol mixture according to the invention may contain alcoholmolecules having different carbon numbers. The carbon numbers of thealcohols in an alcohol mixture may be determined using the methodsdescribed in WO 2006/012989. From such an analysis, an average carbonnumber, typically averaged on a weight basis, for the alcohol mixturemay be determined. We prefer to produce an alcohol having an averagecarbon number in the range of from 8 to 10.5, preferably from 8.5 to9.5. We prefer the mixture to contain at least 90 wt % of alcoholshaving from 8 to 11 carbon atoms, most preferably from 9 to 10 carbonatoms.

The alcohols produced by the present invention may be used in theproduction of esters. The esters are prepared by esterification of acidsand/or their anhydrides with the alcohols of the invention.

The esterification process comprises the following steps: a) adding theacid and/or anhydride and an excess of the alcohols to a reactionvessel; and b) heating the reaction mixture to a temperature at about orabove the boiling point of the alcohol and maintaining a pressuresufficient to obtain boiling of the reaction mixture. The acid and/oranhydride and the alcohols are thereby converted to an ester. Water andsome of the unreacted alcohol are removed from the reaction vessel andthe alcohol removed may be recycled to the vessel.

The esterification process is preferably conducted in the presence of acatalyst. Typical esterification catalysts of commercial importance aresulfuric acid, methane sulfonic acid (MSA), para-toluene sulfonic acid(pTSA), stannous alcoholates or oxides, and titanium alcoholates. U.S.Pat. No. 3,056,818 discloses titanium esterification catalysts and isincorporated herein by reference, the more commonly used catalysts beingtetra-isopropyl titanate and/or tetra-octyl titanate including tetraiso-octyl titanate More details on how the esterification process may beconducted, may be found in U.S. Pat. Nos. 5,324,853, 5,880,310 and6,355,817, and particularly in WO 2005/021482, WO 2006/125670, WO2008/110305 and WO 2008/110306, which are incorporated herein byreference.

The esterification process may further include one or more of thefollowing steps: removing excess alcohol by nitrogen or steam stripping;adding adsorbents such as alumina, silica gel, activated carbon, clayand/or filter aid to the reaction mixture following esterificationbefore further treatment; adding water and base to simultaneouslyneutralise the residual organic acids and to hydrolyse the catalyst (ifpresent); filtering off solids from the ester mixture containing thebulk of the excess alcohol; removing water by flashing or steam ornitrogen stripping under vacuum and recycling of the alcohol or acidinto the reaction vessel; and removing solids from the stripped ester ina final filtration.

In another embodiment, the invention provides for a process furthercomprising the esterification of the alcohol product or product mixturewith an acid or anhydride to form an ester. The acid or anhydride ispreferably selected from the group consisting of benzoic acid, phthalicacid, adipic acid, trimellitic acid, cyclohexanoic acid, cyclohexanoicdibasic acid, pyromellitic acid and their anhydrides. Particularly thephthalate esters, typically produced from phthalic anhydride, are ofsignificant commercial importance.

The ester molecules produced using the process of the invention maycomprise aromatic rings, such as alkyl benzoates, di-alkyl phthalates ortri-alkyl trimellitates. The aromatic rings in these ester molecules maybe hydrogenated to produce the corresponding cyclohexanoic equivalents,such as mono-alkyl, di-alkyl or tri-alkyl cyclohexanoates. Inparticular, DINP may be further hydrogenated to form di-isononylcyclohexanoate. The process of the invention may therefore be for theproduction of a phthalate di-ester, in particular DINP, and furthercomprise the hydrogenation of the phthalate di-ester to thecorresponding cyclohexanoate, in particular di-isononyl cyclohexanoate.Suitable hydrogenation processes to produce such cyclohexanoates aredisclosed in EP 1042273, U.S. Publication Nos. 2004/0260113,2006/0149097, 2006/0166809, or WO 2004/046078.

In yet another embodiment, the invention therefore provides a processwherein the ester is a phthalate and further comprising thehydrogenation of the phthalate ester to a hexahydrophthalate ester.

Since their introduction in the middle of the 20th century, esters ofC6-C15 alcohols have gained widespread use as plasticisers for PVC. PVCcompounds prepared with phthalate esters of C6-C15 alcohols are used inmany different market segments; these include electrical wireinsulation, flexible vinyl flooring, vinyl coated wallpaper, vinylshower curtains, synthetic leather, vinyl and boat covers, vinylswimming pool liners, vinyl stationary products such as notebook covers,and tarpaulins.

Esters of C9 rich alcohols are often preferred because the C9 estersoffer the best balance of properties when used as plasticisers, such aswith PVC. A variety of other mono, di and tri esters are also known andused as plasticisers for plastics such as PVC.

One of the most important performance characteristics for a plasticiser,when used in PVC compound is its permanence, i.e., its resistance towater extraction, migration and in particular loss by volatility.

In particular, with phthalate esters but also with trimellitates andadipates, the di-alkyl aliphatic (mono-)ester originating from themethyl esters contaminating the alcohol contributes to volatility lossduring processing and use, and especially in fogging performance.

The low content of these di-alkyl aliphatic (mono-)esters thereforebrings improved fogging performance for PVC articles made with theplasticiser esters of the present invention.

Although the C9-rich esters offer advantages over the pure C8 esterswith lower emissions, the level of emission is often not acceptable forsome end-users. For products used in the interior passenger compartmentfor automobiles, manufacturers often develop specifications on themaximum level of emissions which can be released as the automobile sitsin the sun. These emissions can result in the development of a “fog” or“light-scattering-film” that condenses or forms on the inner side of thewindscreen. Currently, no pure C8 phthalate esters and no branched C9phthalate can satisfy the specifications which require a maximal fogformation observed after 3 hours at 100° C. in a fog testing apparatus.To meet these performance criteria, phthalate esters of branched orlinear C10 and C11 alcohols or phthalate esters based on the moreexpensive linear C9 alcohols (such as Jayflex® L9P) or esters oftrimellitic anhydride are used.

There is therefore a continuing need for alcohols which will enable theproduction of plasticisers with an improved balance of properties, inparticular an improved combination of low volatility and low viscosity,and the quality to pass the fog test. Accordingly, the phthalate,cyclohexane dioate, trimellitate and adipate esters of the presentinvention have low fogging properties which are highly desirable for usein automotive interior applications.

Phthalate esters prepared from the alcohol mixture according to thepresent invention provide a PVC plasticiser which has all theperformance advantages associated with conventional phthalate esters,while PVC formulations containing the plasticisers dry-blend faster,i.e., the C8-C10 phthalate mixtures process faster than correspondingformulations containing dioctyl phthalate. When compared to the use ofother known branched phthalate esters as plasticisers for PVC, thephthalate esters according to the present invention provide an improvedcombination of properties including improved processing efficiency,better low temperature performance, lower emission release duringprocessing, as well as lower emission release during the use of theshaped article made from the plasticised PVC (such as fogging). Thanksto the lower volatility, these phthalate esters also provide a lowercontribution to the buildup of Semi-Volatile Organic Compounds (SVOCs)in indoor air. SVOCs are currently defined as compounds boiling in therange delimited by normal hexadecane (n-C16) and up to C40.

Benzoate esters of the particular C8-10 alcohol mixture according to thepresent invention provide a lower contribution to the buildup ofVolatile Organic Compounds (VOCs) in indoor air, as measured by the FLECand Chamber Emission Test, as measured by ENV norm 13419, the VOC testbeing ENV 13419-3 and the FLEC and Chamber Enission test being ENV13419-2. The benzoate esters also bring beneficial effects on the lowtemperature performance of the final flexible PVC article.

The acid or anhydride employed in the production of the esters from thealcohols of the invention is preferably organic. Examples of the organicacid or its anhydride that may be used in the esterification reactioninclude aromatic monocarboxylic acids typified by benzoic acid, andfolic acid; polybasic aromatic carboxylic acids or anhydrides thereof,such as phthalic acid, phthalic anhydride, isophthalic acid,terephthalic acid, trimesic acid, trimellitic acid, trimelliticanhydride, pyromellitic acid, pyromellitic anhydride,benzophenonetetracarboxylic acid and benzo-phenonetetracarboxylicanhydride; polybasic aliphatic carboxylic acids such as adipic acid,sebacic acid and azelaic acid and citric acid; polybasic unsaturatedaliphatic carboxylic acids such as maleic acid and fumaric acid; andaliphatic monocarboxylic acids such as oleic acid and stearic acid. Thevarious phthalic acids or anhydrides are preferred. The alcoholsemployed in the esterification may be used singly or in combination asrequired. C7-C13 alcohols are preferably employed to make plasticiseresters and C9-C11 alcohols, especially the C10 and C11 alcohols arepreferred especially in the production of plasticiser esters.

In one embodiment of the process, the esterification reaction isconducted by adding an alcohol to an organic acid or its anhydride, andreacting the mixture, preferably at from 150° C. to 220° C. andpreferably for from 1 to 4 hours, in the presence of an organic metalcompound catalyst in an inert gas atmosphere while removing waterformed. The reaction time is preferably at the lower end of the range,e.g., from 1.5 to 2 hours, and optimally even less than 1.5 hours. Abase and water, preferably in the form of an aqueous base, is added tothe resulting reaction solution to neutralise any unreacted acid and/ormono-ester and to hydrolyse the catalyst. It is also preferred to removeany free water after the crude ester has been treated with the base andbefore filtration, particularly if the treatment has been with aqueousbase. Preferred bases include alkali metal salts, particularly sodiumsalts, like sodium carbonate, and alkali metal hydroxides, like sodiumhydroxide, e.g., aqueous sodium hydroxide. Any excess alcohol isrecovered typically by stripping (which advantageously removes alcohol,water and other light materials) and the resulting ester product is thenpurified to obtain a plasticiser.

The contaminants in the plasticiser ester may belong to the family ofacidic residues, unreacted alcohol, catalyst residues, water and thecontaminants that were already present in the alcohol feed, most ofthese being so-called monomeric components that are eluted in theso-called “light ends” region of the plasticiser Gas Chromatogram orGC-spectrum, as discussed later. The crude esters may also containbyproducts, such as alcohol (di-alkyl)ethers, benzoate esters,mono-esters from dibasic acids, alcohol oxo acid esters, hemiacetals andvinyl ethers (these are so-called dimeric components and are oftencollectively called “ethers” or “intermediates” due to their elution inthe plasticiser Gas Chromatogram or GC-spectrum between the monomericlight ends and the “trimeric” diesters). Many of these dimericmaterials, as well as acetals which are “trimeric” compounds, may becomehydrolysed during later stages in the process to form odour formers suchas aldehydes and/or other light ends. Methods for the treatment of theesters are described in WO 2005/021482 and WO 2006/125670.

The invention is illustrated by means of the following examples.

EXAMPLES

A C9 hydroformylation product was produced by hydroformylating a mixtureof octenes which was produced by oligomerization of n-butenes overH-ZSM-57 catalyst. The hydroformylation product contained, by weight andas analysed by GC, about 12.3% olefins plus paraffins, 62.7% of thetotal of aldehydes, alcohols and formate esters, 17.9% of acetals and7.1% of other heavies. The hydroformylation product was furthercharacterised by a carbonyl number was 200 mg KOH/g, an acid number of3.22 mg KOH/g, a raw cold sap number of 35.61 mg KOH/g. The net cold sapnumber was thus 32.39 mg KOH/g.

This C9 hydroformylation product was fed at a rate of 440 ml/h, togetherwith a recycle of 800 ml/h of hydro product recycle, to a firsthydrogenation reactor containing 250 ml of sulphided Ni/Mo catalyst,operating at a pressure of 80 barg and a temperature of 180° C., with anexcess hydrogen of 400% and with 2.9 wt % of water in the hydrogenationfeed. The product of the first hydrogenation reactor contained, byweight and as analysed by GC 0.1% of methanol, 12.4% olefins plusparaffins, 80.8% of the sum of aldehydes, alcohols and formate esters,1.1% of acetals and 5.7% of other heavies. The product of thehydrogenation reactor was further characterised by a carbonyl number of6.9 mg KOH/g, an acid number of 5.52 mg KOH/g, a raw cold sap number of10.61 mg KOH/g and a raw hot sap number of 12.15 mg KOH/g. The net coldsap number was thus 10.61−5.52=5.09 mg KOH/g. The total presence ofheavy di-alkyl esters plus methyl esters was thus equivalent to12.15−10.61=1.54 mg KOH/g, and the total loss of valuable moleculesequivalent to 1.54+5.52=7.06 mg KOH/g. The product of the firsthydrogenation reactor contained 161 ppm by weight of methyl esters,mostly methyl nonanoate.

In another experiment the influence of the second hydrogenation step, onresidual methyl esters and on yield loss was evaluated. An experimentperformed over the same catalyst, at 190° C., 120 barg, with a flow of407 ml/h and without any recycle or further water addition. Theexperiment demonstrated that the methyl ester content in the productobtained from the first hydrogenation reactor can be reduced in thesecond hydrogenation reactor by 40%, and that the loss of valuablemolecules, expressed as “min acid make” was reduced by 50%. In addition,the final aldehyde concentration (as measured by carbonyl number) andformate esters (from the net cold sap number) had essentiallydisappeared. The hydrogenation product of the above experiment, when itwould include a second hydrogenation reactor, therefore would contain 97ppm by weight of methyl esters. This hydrogenation product is typicallyforeseen to be distilled, to separate away on one hand olefins plusparaffins as the light oxonation byproduct fraction (LOF), and on theother hand the heavies as heavy oxonation byproduct fraction (HOF)containing most of the acids and the di-alkyl esters. The distillationwould result in the methyl esters being concentrated up into the productalcohol to a level of 97/0.808=120 ppm by weight.

Based on other experiments operating the first hydrogenation reactor onthe same feed, the same flow rates and at the same temperature, but at apressure of 120 barg, it is known that the acid number may be reduced tobelow 3.00 mg KOH/g, and the total loss of valuable molecules may as aresult be reduced to an equivalent of 9.13 mg KOH/g, i.e., less than 75%of the loss obtained when the first hydrogenation reactor was operatingat 80 barg. At the higher pressure, the methyl ester in the firsthydrogenation reactor product would move up to around 225 ppm by weight.After having passed the hydrogenation back end section, thehydrogenation section product would contain about 145 ppm by weight ofmethyl esters. The product alcohol distilled from this hydrogenationsection product would contain about 180 ppm by weight of methyl esters.

Having now fully described this invention, it will be appreciated bythose skilled in the art that the invention can be performed within awide range of parameters within what is claimed, without departing fromthe spirit and scope of the invention.

1. A process for the production of a C₆-C₁₅ alcohol mixture comprisingthe steps of: a. hydroformylating an olefin mixture comprising abranched C₅-C₁₄ olefin to form a hydroformylation product comprisingaldehydes and formate esters, whereby the hydroformylation product has anet cold sap number from 15 to 38 mg KOH/g, and b. converting thealdehydes and formate esters to alcohols in a hydrogenation stepcomprising at least one first hydrogenation reactor comprising a fixedbed of a heterogeneous sulphided bimetallic catalyst, optionally,followed by at least one second hydrogenation reactor connecteddownstream of the first hydrogenation reactor; wherein the feed to thehydrogenation step (b) is a liquid comprising at least a portion of thealdehydes and formate esters formed in step (a) and at least 2% water byweight, based on the liquid hydrogenation feed, and wherein thetemperature in the first hydrogenation reactor is at most 200° C.
 2. Theprocess of claim 1, wherein the temperature in the first hydrogenationreactor is from 150 to 200° C.
 3. The process of claim 1, wherein thetemperature in the first hydrogenation reactor is from 160 to 180° C. 4.The process of claim 1, wherein the process further comprises a secondhydrogenation reactor in step (b) and the temperature in the secondhydrogenation reactor is at least 180° C.
 5. The process of claim 4,wherein the temperature in the second hydrogenation reactor is from 190to 210° C.
 6. The process of claim 1, wherein the amount of water in theliquid feed to step (b) is from 2 to 3% by weight.
 7. The process ofclaim 1, wherein the pressure in the first hydrogenation reactor is atleast 55 barg.
 8. The process of claim 1, wherein the pressure in thefirst hydrogenation reactor is at least 60 barg.
 9. The process of claim1, wherein the pressure in the first hydrogenation reactor is at least120 barg.
 10. The process of claim 1, wherein the pressure in the firsthydrogenation reactor is at least 125 barg.
 11. The process of claim 1,wherein the pressure in the first hydrogenation reactor is from 55 to130 barg.
 12. The process of claim 1, wherein the heterogeneoussulphided bimetallic catalyst is selected from the group consisting ofsulphided Co oxide/Mo oxide, sulphided Ni/W, sulphided Ni oxide/Mooxide, and mixtures thereof.
 13. The process of claim 1, wherein thehydrogenation step (b) is preceded by a step to reduce the level offormate esters in the liquid feed to hydrogenation step (b).
 14. Theprocess of claim 13, wherein the level of formate esters is reduced byhydrolysis.
 15. The process of claim 13, wherein the level of formateesters is reduced by contacting the liquid feed with a cuprous chromecatalyst in the presence of hydrogen and at least 2% by weight of water,based on the total liquid feed to the hydrogenation step (b).
 16. Theprocess of claim 1, wherein the process further comprises a secondhydrogenation reactor in step (b) and when the activity of the catalystin the first hydrogenation reactor has decreased to below its initialactivity, a third hydrogenation reactor comprising a heterogeneoussulphided bimetallic catalyst having a higher activity than the catalystin the first hydrogenation reactor is introduced into service locatedupstream of the first hydrogenation reactor.
 17. The process of claim16, wherein, subsequently to the introduction of the third hydrogenationreactor, the first or the second hydrogenation reactor is removed fromservice, optionally, followed by regenerating the catalyst in thereactor removed from service or replacing the catalyst in the reactorremoved from service with a regenerated and/or a fresh catalyst.
 18. Theprocess of claim 1, wherein the process further comprises esterifyingthe C₆-C₁₅ alcohol mixture with an acid or anhydride to form an ester.19. The process of claim 18, wherein the acid or anhydride is selectedfrom the group consisting of benzoic acid, phthalic acid, adipic acid,trimellitic acid, cyclohexanoic acid, cyclohexanoic dibasic acid,pyromellitic acid, any of the aforementioned acids' anhydrides, andmixtures thereof.
 20. The process of claim 18, wherein the ester is aphthalate ester.
 21. The process of claim 20, wherein the processfurther comprises hydrogenating the aromatic ring of the phthalateester.